Elemental base pressure-dependent reactions

Very recently, Hu et al. claimed to have discovered a convenient procedure for the aerobic oxidation of primary and secondary alcohols utilizing a TEMPO based catalyst system free of any transition metal co-catalyst (21). These authors employed a mixture of TEMPO (1 mol%), sodium nitrite (4-8 mol%) and bromine (4 mol%) as an active catalyst system. The oxidation took place at temperatures between 80-100 °C and at air pressure of 4 bars. However, this process was only successful with activated alcohols. With benzyl alcohol, quantitative conversion to benzaldehyde was achieved after a 1-2 hour reaction. With non-activated aliphatic alcohols (such as 1-octanol) or cyclic alcohols (cyclohexanol), the air pressure needed to be raised to 9 bar and a 4-5 hour of reaction was necessary to reach complete conversion. Unfortunately, this new oxidation procedure also depends on the use of dichloromethane as a solvent. In addition, the elemental bromine used as a cocatalyst is rather difficult to handle on a technical scale because of its high vapor pressure, toxicity and severe corrosion problems. Other disadvantages of this system are the rather low substrate concentration in the solvent and the observed formation of bromination by-products. 

A vortex tube has certain advantages as a chemical reactor, especially if the reactions are endothermic, the reaction pathways are temperature dependent, and the products are temperature sensitive. With low temperature differences, the vortex reactor can transmit enormous heat fluxes to a process stream containing entrained solids. This reactor is ideally suited for the production of pyrolysis oils from biomass at low pressures and residence times to produce about 10 wt % char, 13% water, 7% gas, and 70% oxygenated primary oil vapors based on mass balances. This product distribution was verified by carbon, hydrogen, and oxygen elemental balances. The oil production appears to form by fragmenting all of the major constituents of the biomass. 

---